A Comprehensive Emission Inventory of Bbiogenic Volatile Organic Compounds in Europe: Improved Seasonality and Land-cover

Biogenic volatile organic compounds (BVOC) emitted from vegetation are important for the formation of secondary pollutants such as ozone and secondary organic aerosols (SOA) in the atmosphere. Therefore, BVOC emission are an important input for air quality models. To model these emissions with high spatial resolution, the accuracy of the underlying vegetation inventory is crucial. We present a BVOC emission model that accommodates different vegetation inventories and uses satellite-based measurements of greenness instead of pre-defined vegetation periods. This approach to seasonality implicitly treats effects caused by water or nutrient availability, altitude and latitude on a plant stand. Additionally, we test the influence of proposed seasonal variability in enzyme activity on BVOC emissions. In its present setup, the emission model calculates hourly emissions of isoprene, monoterpenes, sesquiterpenes and the oxygenated volatile organic compounds (OVOC) methanol, formaldehyde, formic acid, ethanol, acetaldehyde, acetone and acetic acid. In this study, emissions based on three different vegetation inventories are compared with each other and diurnal and seasonal variations in Europe are investigated for the year 2006. Two of these vegetation inventories require information on tree-cover as an input. We compare three different land-cover inventories (USGS GLCC, GLC2000 and Globcover 2.2) with respect to tree-cover. The often-used USGS GLCC land-cover inventory leads to a severe reduction of BVOC emissions due to a potential miss-attribution of broad-leaved trees and reduced tree-cover compared to the two other land-cover inventories. To account for uncertainties in the land-cover classification, we introduce land-cover correction factors for each relevant land-use category to adjust the tree-cover. The results are very sensitive to these factors within the plausible range. For June 2006, total monthly BVOC emissions decreased up to −27% with minimal and increased up to +71% with maximal factors, while in January 2006, the changes in monthly BVOC emissions were −54 and +56% with minimal and maximal factors, respectively. The new seasonality approach leads to a reduction in the annual emissions compared with non-adjusted data. The strongest reduction occurs in OVOC (up to −32 %), the weakest in isoprene (as little as −19 %). If also enzyme seasonality is taken into account, however, isoprene reacts with the steepest decrease of annual emissions, which are reduced by −44% to −49 %, annual emissions of monoterpenes reduce between −30 and −35 %. The sensitivity of the model to changes in temperature depends on the climatic zone but not on the vegetation inventory. The sensitivity is higher for temperature increases of 3K (+31% to +64 %) than decreases by the same amount (−20 to −35 %). The climatic zones “Cold except summer” and “arid” are most sensitive to temperature changes in January for isoprene and monoterpenes, respectively, while in June, “polar” is most sensitive to temperature for both isoprene and monoterpenes. Our model predicts the oxygenated volatile organic compounds to be the most abundant fraction of the annual European emissions (3571–5328 Gg yr−1), followed by monoterpenes (2964–4124 Gg yr−1), isoprene (1450–2650 Gg yr−1) and sesquiterpenes (150–257 Gg yr−1). We find regions with high isoprene emissions (most notably the Iberian Peninsula), but overall, oxygenated VOC dominate with 43–45% (depending on the vegetation inventory) contribution to the total annual BVOC emissions in Europe. Isoprene contributes between 18–21 %, monoterpenes 33–36% and sesquiterpenes contribute 1–2 %.We compare the concentrations of biogenic species simulated by an air quality model with measurements of isoprene and monoterpenes in Hohenpeissenberg (Germany) for both summer and winter. The agreement between observed and modelled concentrations is better in summer than in winter. This can partly be explained with the difficulty to model weather conditions in winter accurately, but also with the increased anthropogenic influence on the concentrations of BVOC compounds in winter. Our results suggest that land-cover inventories used to derive tree-cover must be chosen with care. Also, uncertainties in the classification of land-cover pixels must be taken into account and remain high. This problem must be addressed together with the remote sensing community. Our new approach using a greenness index for addressing seasonality of vegetation can be implemented easily in existing models. The importance of OVOC for air quality should be more deeply addressed by future studies, especially in smog chambers. Also, the fate of BVOC from the dominant region of the Iberian Peninsula should be studied more in detail

Volatile Organic Compounds in the Po Basin. Part B: Biogenic VOCs

Measurements of volatile organic compounds (VOCs) were performed in the Po Basin, northern Italy in early summer 1998, summer 2002, and autumn 2003. During the three campaigns, trace gases and meteorological parameters were measured at a semi-rural station, around 35 km north of the city center of Milan. Bimodal diurnal cycles of isoprene with highest concentrations in the morning and evening were found and could be explained by the interaction of emissions, chemical reactions, and vertical mixing. The diurnal cycle could be qualitatively reproduced by a three-dimensional Eulerian model. The nighttime decay of isoprene could be attributed mostly to reactions with NO3, while the decay of the isoprene oxidation products could not be explained with the considered chemical reactions. Methanol reached very high mixing ratios, up to 150 ppb. High concentrations with considerable variability occurred during nights with high relative humidities and low wind speeds. The origin of these nighttime methanol concentrations is most likely local and biogenic but the specific source could not be identifie

Modelling winter organic aerosol at the European scale with CAMx : evaluation and source apportionment with a VBS parameterization based on novel wood burning smog chamber experiments

We evaluated a modified VBS (volatility basis set) scheme to treat biomass-burning-like organic aerosol (BBOA) implemented in CAMx (Comprehensive Air Quality Model with extensions). The updated scheme was parameterized with novel wood combustion smog chamber experiments using a hybrid VBS framework which accounts for a mixture of wood burning organic aerosol precursors and their further functionalization and fragmentation in the atmosphere. The new scheme was evaluated for one of the winter EMEP intensive campaigns (February March 2009) against aerosol mass spectrometer (AMS) measurements performed at 11 sites in Europe. We found a considerable improvement for the modelled organic aerosol (OA) mass compared to our previous model application with the mean fractional bias (MFB) reduced from 61 to 29 %. We performed model-based source apportionment studies and compared results against positive matrix factorization (PMF) analysis performed on OA AMS data. Both model and observations suggest that OA was mainly of secondary origin at almost all sites. Modelled secondary organic aerosol (SOA) contributions to total OA varied from 32 to 88 % (with an average contribution of 62 %) and absolute concentrations were generally under-predicted. Modelled primary hydrocarbon-like organic aerosol (HOA) and primary biomass-burning-like aerosol (BBPOA) fractions contributed to a lesser extent (HOA from 3 to 30 %, and BBPOA from 1 to 39 %) with average contributions of 13 and 25 %, respectively. Modelled BBPOA fractions were found to represent 12 to 64 % of the total residential-heating-related OA, with increasing contributions at stations located in the northern part of the domain. Source apportionment studies were performed to assess the contribution of residential and non-residential combustion precursors to the total SOA. Non-residential combustion and road transportation sector contributed about 30-40 % to SOA formation (with increasing contributions at urban and near industrialized sites), whereas residential combustion (mainly related to wood burning) contributed to a larger extent, around 60-70 %. Contributions to OA from residential combustion precursors in different volatility ranges were also assessed: our results indicate that residential combustion gas-phase precursors in the semivolatile range (SVOC) contributed from 6 to 30 %, with higher contributions predicted at stations located in the southern part of the domain On the other hand, the oxidation products of higher-volatility precursors (the sum of intermediate-volatility compounds (IVOCs) and volatile organic compounds (VOCs)) contribute from 15 to 38 % with no specific gradient among the stations. Although the new parameterization leads to a better agreement between model results and observations, it still under predicts the SOA fraction, suggesting that uncertainties in the new scheme and other sources and/or formation mechanisms remain to be elucidated. Moreover, a more detailed characterization of the semivolatile components of the emissions is needed.Peer reviewe

Evaluation of European air quality modelled by CAMx including the volatility basis set scheme

Four periods of EMEP (European Monitoring and Evaluation Programme) intensive measurement campaigns (June 2006, January 2007, September-October 2008 and February-March 2009) were modelled using the regional air quality model CAMx with VBS (volatility basis set) approach for the first time in Europe within the framework of the EURODELTA-III model intercomparison exercise. More detailed analysis and sensitivity tests were performed for the period of February-March 2009 and June 2006 to investigate the uncertainties in emissions as well as to improve the modelling of organic aerosol (OA). Model performance for selected gas phase species and PM2.5 was evaluated using the European air quality database AirBase. Sulfur dioxide (SO2) and ozone (O-3) were found to be overestimated for all the four periods, with O-3 having the largest mean bias during June 2006 and January-February 2007 periods (8.9 pbb and 12.3 ppb mean biases respectively). In contrast, nitrogen dioxide (NO2) and carbon monoxide (CO) were found to be underestimated for all the four periods. CAMx reproduced both total concentrations and monthly variations of PM2.5 for all the four periods with average biases ranging from -2.1 to 1.0 mu g m(-3). Comparisons with AMS (aerosol mass spectrometer) measurements at different sites in Europe during February-March 2009 showed that in general the model overpredicts the inorganic aerosol fraction and underpredicts the organic one, such that the good agreement for PM2.5 is partly due to compensation of errors. The effect of the choice of VBS scheme on OA was investigated as well. Two sensitivity tests with volatility distributions based on previous chamber and ambient measurements data were performed. For February-March 2009 the chamber case reduced the total OA concentrations by about 42% on average. In contrast, a test based on ambient measurement data increased OA concentrations by about 42% for the same period bringing model and observations into better agreement. Comparison with the AMS data at the rural Swiss site Payerne in June 2006 shows no significant improvement in modelled OA concentration. Further sensitivity tests with increased biogenic and anthropogenic emissions suggest that OA in Payerne was affected by changes in emissions from residential heating during the February-March 2009 whereas it was more sensitive to biogenic precursors in June 2006.Peer reviewe

Photochemical modelling in the Po basin with focus on formaldehyde and ozone

As part of the EU project FORMAT ( Formaldehyde as a Tracer of Oxidation in the Troposphere), a field campaign was carried out in the vicinity of Milan during the summer of 2002. Results from a 3-D regional chemical transport model (NILU RCTM) were used to interpret the observations focusing primarily on HCHO and ozone. The performance of the model was assessed by comparing model results with ground based and aircraft measurements. The model results show good agreement with surface measurements, and the model is able to reproduce the photochemical episodes during fair weather days. The comparison indicates that the model can represent well the HCHO concentrations as well as their temporal and spatial variability. The relationship between HCHO and (O-3 x H2O) was used to validate the model ability to predict the HCHO concentrations. Further analysis revealed the importance of the representativeness of different instruments: in-situ concentrations might be locally enhanced by emissions, while long path measurements over a forest can be influenced by rapid formation of HCHO from isoprene. The model is able to capture the plume from the city of Milan and the modelled levels agree generally well with the aircraft measurements, although the wind fields used in the model can lead to a displacement of the ozone plume. During the campaign period, O3 levels were seldom higher than 80 ppb, the peak surface ozone maxima reached 90 ppb. Those relatively low values can be explained by low emissions during the August vacation and unstable weather conditions in this period. The modelled Delta O-3/Delta NOz slope at Alzate of 5.1 agrees well with the measured slope of 4.9

Role of ammonia in European air quality with changing land and ship emissions between 1990 and 2030

The focus of this modeling study is on the role of ammonia in European air quality in the past as well as in the future. Ammonia emissions have not decreased as much as the other secondary inorganic aerosol (SIA) precursors – nitrogen oxides (NOx) and sulfur dioxide (SO2) – since the 1990s and are still posing problems for air quality and the environment. In this study, air quality simulations were performed with a regional chemical transport model at decadal intervals between 1990 and 2030 to understand the changes in the chemical species associated with SIA under varying land and ship emissions. We analyzed the changes in air concentrations of ammonia, nitric acid, ammonium, particulate nitrate and sulfate as well as changes in the dry and wet deposition of ammonia and ammonium. The results show that the approximately 40 % decrease in SIA concentrations between 1990 and 2010 was mainly due to reductions in NOx and SO2 emissions. The ammonia concentrations on the other hand decreased only near the high-emission areas such as the Netherlands and northern Italy by about 30 %, while there was a slight increase in other parts of Europe. Larger changes in concentrations occurred mostly during the first period (1990–2000). The model results indicate a transition period after 2000 for the composition of secondary inorganic aerosols due to a larger decrease in sulfate concentrations than nitrate. Changes between 2010 and 2030 – assuming the current legislation (CLE) scenario – are predicted to be smaller than those achieved earlier for all species analyzed in this study. The scenario simulations suggest that if ship emissions will be regulated more strictly in the future, SIA formation will decrease especially around the Benelux area, North Sea, Baltic Sea, English Channel and the Mediterranean region, leaving more ammonia in the gas phase, which would lead to an increase in dry deposition. In the north of the domain, the decrease in SIA would be mainly due to reduced formation of particulate nitrate, while the change around the Mediterranean would be caused mainly by decreased sulfate aerosol concentrations. One should also keep in mind that potentially higher temperatures in the future might increase the evaporation of ammonium nitrate to form its gaseous components NH3 and HNO3. Sensitivity tests with reduced NOx and NH3 emissions indicate a shift in the sensitivity of aerosol formation from NH3 towards NOx emissions between 1990 and 2030 in most of Europe except the eastern part of the model domain.The focus of this modeling study is on the role of ammonia in European air quality in the past as well as in the future Ammonia emissions have not decreased as much as the other secondary inorganic aerosol (SIA) precursors - nitrogen oxides (NOx) and sulfur dioxide (SO2) - since the 1990s and are still posing problems for air quality and the environment. In this study, air quality simulations were performed with a regional chemical transport model at decadal intervals between 1990 and 2030 to understand the changes in the chemical species associated with SIA under varying land and ship emissions. We analyzed the changes in air concentrations of ammonia, nitric acid, ammonium, particulate nitrate and sulfate as well as changes in the dry and wet deposition of ammonia and ammonium. The results show that the approximately 40 % decrease in SIA concentrations between 1990 and 2010 was mainly due to reductions in NOx and SO2 emissions. The ammonia concentrations on the other hand decreased only near the high-emission areas such as the Netherlands and northern Italy by about 30 %, while there was a slight increase in other parts of Europe. Larger changes in concentrations occurred mostly during the first period (1990-2000). The model results indicate a transition period after 2000 for the composition of secondary inorganic aerosols due to a larger decrease in sulfate concentrations than nitrate. Changes between 2010 and 2030 - assuming the current legislation (CLE) scenario - are predicted to be smaller than those achieved earlier for all species analyzed in this study. The scenario simulations suggest that if ship emissions will be regulated more strictly in the future, SIA formation will decrease especially around the Benelux area, North Sea, Baltic Sea, English Channel and the Mediterranean region, leaving more ammonia in the gas phase, which would lead to an increase in dry deposition. In the north of the domain, the decrease in SIA would be mainly due to reduced formation of particulate nitrate, while the change around the Mediterranean would be caused mainly by decreased sulfate aerosol concentrations. One should also keep in mind that potentially higher temperatures in the future might increase the evaporation of ammonium nitrate to form its gaseous components NH3 and HNO3. Sensitivity tests with reduced NOx and NH3 emissions indicate a shift in the sensitivity of aerosol formation from NH3 towards NOx emissions between 1990 and 2030 in most of Europe except the eastern part of the model domain.Peer reviewe

Sorption of Cesium and Strontium on Montmorillonite and Kaolinite

Sorption characteristics of Cs+ and Sr++on montmorillonite and kaolinite type clays and soil fractions from various regions of Turkey were studied using the batch method. 137Cs and 90Sr were used as tracers. Concentrations of Cs+ and Sr++ ions ranged from 10-8to 10-2 mol/1; natural groundwater was used and the grain size of the solid particles was < 20 yμm. Equilibrium was reached in 4 - 7 days for Cs+and 7 - 11 days for Sr++. The distribution coefficient, RD, increased with decreasing grain size, suggesting mainly a surface phenomenon. The sorption isotherms were non-linear suggesting at least two different sorption processes. The sorption was found to be predominantly reversible. Cs+ was sorbed much stronger than Sr++in all samples. © 1988, Walter de Gruyter. All rights reserved

Constraining a hybrid volatility basis-set model for aging of wood-burning emissions using smog chamber experiments : A box-model study based on the VBS scheme of the CAMx model (v5.40)

In this study, novel wood combustion aging experiments performed at different temperatures (263 and 288 K) in a ∼ 7 m³ smog chamber were modelled using a hybrid volatility basis set (VBS) box model, representing the emission partitioning and their oxidation against OH. We combine aerosol–chemistry box-model simulations with unprecedented measurements of non-traditional volatile organic compounds (NTVOCs) from a high-resolution proton transfer reaction mass spectrometer (PTR-MS) and with organic aerosol measurements from an aerosol mass spectrometer (AMS). Due to this, we are able to observationally constrain the amounts of different NTVOC aerosol precursors (in the model) relative to low volatility and semi-volatile primary organic material (OM$_{sv}$), which is partitioned based on current published volatility distribution data. By comparing the NTVOC ∕ OM$_{sv}$ ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass-burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30 000 box-model simulations were performed to retrieve the combination of parameters that best fit the observed organic aerosol mass and O : C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O : C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ∼ 4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA) concentrations were predicted to vary between 8 and 30 % after 5 h of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10$^{-11}$ to 4. 0 × 10$^{-11}$ cm³ molec$^{-1}$ s$^{-1}$. The average enthalpy of vaporization of secondary organic aerosol (SOA) surrogates was determined to be between 55 000 and 35 000 J mol$^{-1}$, which implies a yield increase of 0.03-0.06 % K$^{-1}$ with decreasing temperature. The improved VBS scheme is suitable for implementation into chemical transport models to predict the burden and oxidation state of primary and secondary biomass-burning aerosols

Solar “brightening” impact on summer surface ozone between 1990 and 2010 in Europe – a model sensitivity study of the influence of the aerosol–radiation interactions

Surface solar radiation (SSR) observations have indicated an increasing trend in Europe since the mid-1980s, referred to as solar brightening. In this study, we used the regional air quality model, CAMx (Comprehensive Air Quality Model with Extensions) to simulate and quantify, with various sensitivity runs (where the year 2010 served as the base case), the effects of increased radiation between 1990 and 2010 on photolysis rates (with the PHOT1, PHOT2 and PHOT3 scenarios, which represented the radiation in 1990) and biogenic volatile organic compound (BVOC) emissions (with the BIO scenario, which represented the biogenic emissions in 1990), and their consequent impacts on summer surface ozone concentrations over Europe between 1990 and 2010. The PHOT1 and PHOT2 scenarios examined the effect of doubling and tripling the anthropogenic PM2.5 concentrations, respectively, while the PHOT3 investigated the impact of an increase in just the sulfate concentrations by a factor of 3.4 (as in 1990), applied only to the calculation of photolysis rates. In the BIO scenario, we reduced the 2010 SSR by 3 % (keeping plant cover and temperature the same), recalculated the biogenic emissions and repeated the base case simulations with the new biogenic emissions. The impact on photolysis rates for all three scenarios was an increase (in 2010 compared to 1990) of 3–6 % which resulted in daytime (10:00–18:00 Local Mean Time – LMT) mean surface ozone differences of 0.2–0.7 ppb (0.5–1.5 %), with the largest hourly difference rising as high as 4–8 ppb (10–16 %). The effect of changes in BVOC emissions on daytime mean surface ozone was much smaller (up to 0.08 ppb,  ∼  0.2 %), as isoprene and terpene (monoterpene and sesquiterpene) emissions increased only by 2.5–3 and 0.7 %, respectively. Overall, the impact of the SSR changes on surface ozone was greater via the effects on photolysis rates compared to the effects on BVOC emissions, and the sensitivity test of their combined impact (the combination of PHOT3 and BIO is denoted as the COMBO scenario) showed nearly additive effects. In addition, all the sensitivity runs were repeated on a second base case with increased NOx emissions to account for any potential underestimation of modeled ozone production; the results did not change significantly in magnitude, but the spatial coverage of the effects was profoundly extended. Finally, the role of the aerosol–radiation interaction (ARI) changes in the European summer surface ozone trends was suggested to be more important when comparing to the order of magnitude of the ozone trends instead of the total ozone concentrations, indicating a potential partial damping of the effects of ozone precursor emissions' reduction.</p

Aerosol modelling in Europe with a focus on Switzerland during summer and winter episodes

This paper describes aerosol modelling in Europe with a focus on Switzerland during summer and winter periods. We modelled PM&lt;sub&gt;2.5&lt;/sub&gt; (particles smaller than 2.5 μm in aerodynamic diameter) for one summer and two winter periods in years 2006 and 2007 using the CAMx air quality model. The meteorological fields were obtained from MM5 simulations. The modelled wind speeds during some low-wind periods, however, had to be calibrated with measurements to use realistic input for the air quality model. The detailed AMS (aerosol mass spectrometer) measurements at specific locations were used to evaluate the model results. In addition to the base case simulations, we carried out sensitivity tests with modified aerosol precursor emissions, air temperature and deposition. Aerosol concentrations in winter 2006 were twice as high as those in winter 2007, however, the chemical compositions were similar. CAMx could reproduce the relative composition of aerosols very well both in the winter and summer periods. Absolute concentrations of aerosol species were underestimated by about 20 %. Both measurements and model results suggest that organic aerosol (30–38 %) and particulate nitrate (30–36 %) are the main aerosol components in winter. In summer, organic aerosol dominates the aerosol composition (55–57 %) and is mainly of secondary origin. The contribution of biogenic volatile organic compound (BVOC) emissions to the formation of secondary organic aerosol (SOA) was predicted to be very large (&gt;95 %) in Switzerland. The main contributors to the modelled SOA concentrations were oxidation products of monoterpenes and sesquiterpenes as well as oligomerization of oxidized compounds. The fraction of primary organic aerosol (POA) derived from measurements was lower than the model predictions indicating the importance of volatility of POA, which has not yet been taken into account in CAMx. Sensitivity tests with reduced NO&lt;sub&gt;x&lt;/sub&gt; and NH&lt;sub&gt;3&lt;/sub&gt; emissions suggest that aerosol formation is more sensitive to ammonia emissions in winter in a large part of Europe. In Switzerland however, aerosol formation is predicted to be NO&lt;sub&gt;x&lt;/sub&gt;-sensitive. In summer, effects of NO&lt;sub&gt;x&lt;/sub&gt; and NH&lt;sub&gt;3&lt;/sub&gt; emission reductions on aerosol concentrations are predicted to be lower mostly due to lower ammonium nitrate concentrations. In general, the sensitivity to NH&lt;sub&gt;3&lt;/sub&gt; emissions is weaker in summer due to higher NH&lt;sub&gt;3&lt;/sub&gt; emissions